The photocatalytic (PC) and photoelectrocatalytic (PEC) properties of WO 3 /BiVO 4 photo-anode for organic dye degradation under visible light irradiation were studied. The performance of the electrodes was investigated by monitoring the % degradation of methylene blue (MB) as a dye sample with UV–vis spectroscopy. To study the charge transfer rate improvement, a Cu 2 O electrode was employed as a photo-cathode. In addition, Ag nanoparticles were deposited on both WO 3 /BiVO 4 and Cu 2 O electrodes to study the effect on the catalytic activity for MB degradation. SEM, XRD and XPS techniques were used to confirm the morphologies and composition of the modified electrodes. The effects of pH and the irradiation wavelengths were investigated to understand the condition of MB degradation process. The highest performance for MB degradation was attained when WO 3 /BiVO 4 was used as a photo-anode and Cu 2 O/Ag as a photo-cathode under the PEC process.